06.09.

2017 Band Structure D agrams

Band Structure D agrams

Why should chem sts care about band structure d agrams?

Thus far we have d scussed molecular orb tal (MO) d agrams n some deta l. These descr be the
electron c energy levels of solated molecules. As we have d scussed they also can be used to
approx mate the energy levels n a sol d. However, n a sol d ntermolecular (between
ne ghbor ng molecules) nteract ons can also be mportant. In fact many nterest ng propert es of
sol ds such as metall c conduct v ty, superconduct v ty, magnet sm, etc. depend cruc ally upon
ntermolecular nteract ons.

The sol d state equ valent to a MO d agram s called a band structure d agram. The band
structure d agram conta ns nformat on about both the bond ng nteract ons w th n a molecule
( ntramolecular) and the ntermolecular nteract ons. Chem sts often refer to band structure
d agrams as spaghett plots, because or the r appearance. However, the ab l ty to understand band
structure d agrams allows one to extract valuable nformat on about a mater al:

Electron c conduct v ty
Opt cal propert es
Stab l ty of a compound toward ox dat on or reduct on (dop ng)

In th s way knowledge of the electron c band structure prov des pred ct ve ns ght and
understand ng of certa n very mportant phys cal propert es of sol ds. Furthermore, just as the
energy levels n a MO d agram are dependent upon the energy levels of the atom c orb tals as
well as the symmetry and nteratom c d stances n a molecule, the electron c band structure s
dependent upon energy levels of the const tuent atom c orb tals and the crystal structure. Th s
br ngs us to a very mportant po nt:

The electron c band structure of a mater al s the key l nk between ts crystal structure and
phys cal propert es. Therefore, sol d state chem sts who hope to explore structure-property
relat onsh ps n mater als should be able to understand the or g n of band structure n chem cal
terms.

An add t onal mot vat on to understand band structures s g ven by the fact that such knowledge
s often needed to effect vely commun cate w th condensed matter phys c sts, many of whom are
very good at calculat ng band structures. A rough compar son of the way chem sts and phys c sts
v ew sol ds s g ven n the table below.

Chem st Phys c st

Local zed electrons Delocal zed electrons

MO D agram Band Structure D agram

Molecular Orb tal Wavevector

Chem cal bond ng Potent als

Qual tat ve (Intu t ve) Quant tat ve (Mathemat cal)

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06.09.2017 Band Structure D agrams

Sc ent sts who are able to see both po nts of v ew tend to have great ns ght nto the behav or of
sol d state mater als.

The purpose of the rest of th s lecture s an attempt to understand band structure d agrams n
terms of bas c chem cal bond ng nteract ons. The treatment s very s m lar to the excellent
descr pt on g ven by Roald Hoffmann n h s book, "Sol ds and Surfaces: A Chem sts V ew of
Bond ng n Extended Structures."

The Band Structure of a 1D cha n of H atoms

Lets beg n by construct ng the band structure, wh ch corresponds to the s mplest system we can
th nk of, a 1D cha n of hydrogen atoms.

If there are N atoms n the cha n there w ll be N energy levels and N electron c states ("MOs").
The wavefunct on for each electron c state s

Yk = S e kna cn

where a s the latt ce constant (spac ng between H atoms) and n s a counter for each atom c
orb tal n the cha n. Not ce that each Yk s really just a symmetry adapted l near comb nat on
(SALC) of AO�s, where the symmetry operator n th s case s translat onal symmetry.

The var able k can be thought of as an ndex wh ch labels the respect ve SALC�s, t also tells us
the phase of the orb tals as the follow ng f gure llustrates:

At k=0 all of the orb tals are n phase, wh le at k = p/a the orb tals are out of phase, at
ntermed ate values the phase of the orb tals var es (the wavelength of the phase var at on s
g ven by the denom nator .e. a, 2a, etc.).

Remarkably the value of k also s related to the wavelength of the wavepacket wh ch descr bes
an electron n a g ven state, Yk, by the relat onsh p:

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06.09.2017 Band Structure D agrams

l = 2p/k

We w ll return to th s relat onsh p later when we d scuss electron c conduct v ty.

It should be ntu t vely obv ous that of all the poss ble states, Yk, the bond ng comb nat on at k =
0 w ll have the lowest energy and the ant bond ng comb nat on at k = p/a w ll have the h ghest
energy. States n between such as k = p/2a w ll be ntermed ate. Keep ng these th ngs n m nd we
can draw an approx mate band structure d agram for th s very s mple system.

Desp te ts s mpl c ty there are features of th s band structure d agram that we can learn from

(1) The band runs "uph ll" (from 0 to p/a) because the n phase (at k=0) comb nat on of orb tals
s bond ng and the out of phase (at k=p/a) s ant bond ng. If one were to cons der a s gma
nteract on of p orb tals, the oppos te s tuat on would hold and the band would run "downh ll".

(2) As the orb tal overlap s ncreased (for example by decreas ng the nteratom c spac ng) the
bond ng nteract on s further stab l zed wh le the ant bond ng s further destab l zed. Th s w ll
cause the band w dth to ncrease. Keep n m nd though, that because the ant bond ng
destab l zat on s larger than the bond ng stab l zat on the top of the band w ll r se more than the
bottom w ll s nk.

Small overlap ® narrow bands ® local zed electrons

Large overlap ® w de bands ® delocal zed electrons

For a more thorough descr pt on of these effects refer to e ther your class notes, or to
Hoffmann�s book (Sol ds and Surfaces).

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06.09.2017 Band Structure D agrams

The Ferm level � Metals, Sem conductors and Insulators

The dashed l ne n the hydrogen cha n band structure represents the energy of the h ghest f lled
state (HOMO). Th s energy level s called the Ferm level, EF. Depend ng upon the pos t on of
EF we can make several mportant d st nct ons regard ng the expected electr cal conduct v ty of a
mater al. Keep n m nd that a real band structure d agram would have many d fferent bands, but
only one Ferm level

Metal � EF cuts through a band.

Sem conductor/Insulator � EF does not ntersect a band.

The d st nct on between a sem conductor and an nsulator s somewhat arb trary. In e ther case,
each band w ll be e ther completely full or completely empty (at T = 0 K anyway). Therefore,
electrons cannot move from one state to another w th an nf n tes mal amount of energy as they
can n metals, they have to be exc ted across an energy gap before conduct v ty can occur. The
magn tude of th s gap s the energy d fference between the most energet c state among the f lled
bands (valence band, VB) and the lowest energy state among the empty bands (conduct on band,
CB). It s called the band gap, Eg. One arb trary d st nct on wh ch s somet mes used s to say
that sem conductors have Eg < 3 eV, wh le nsulators have Eg > 3 eV, although others may use a
d fferent d st nct on.

Pe erls D stort on to Form H2

Because the Ferm level cuts through a band we expect a l near cha n of equally spaced hydrogen
atoms to be a metall c conductor. However, t should be mmed ately obv ous to a chem st that
th s system s not stable w th respect to d mer zat on (to form H2 molecules). What effect would
such a d stort on have on the band structure?

The un t cell constant would double, a(H2) = 2 a(H), so that 2 hydrogen atoms are now
conta ned w th n the un t cell
S nce there are now 2 atom c orb tals n the un t cell, the band structure d agram w ll
conta n two bands
The s ze of the Br llou n zone (0 < k < p/a) n rec procal space s reduced by a factor of 2,
due to the doubl ng of a

The orb tal nteract ons at var ous k po nts for each band and the band structure d agram are
shown below

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06.09.2017 Band Structure D agrams

These f gures llustrate the follow ng po nts:

The relat ve energy and ntramolecular orb tal nteract ons assoc ated w th each band can
be determ ned from a MO d agram. In th s very s mple example we have a bond ng MO
wh ch leads to the valence band and an ant bond ng MO wh ch leads to the conduct on
band.
Due to the nteract ons between molecules the valence band runs "uph ll" and the
conduct on band runs "downh ll".
There are two electrons per un t cell so that the valence band s full and the conduct on
band empty. Thus EF occup es a pos t on m dway between the two bands and the system s
now a sem conductor/ nsulator.

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06.09.2017 Band Structure D agrams

The m n mum energy gap between bands occurs at k = p/a. S nce the max mum n the VB
and the m n mum n the CB occur at the same value of k, the compound s sa d to be a
d rect gap sem conductor.
Compared w th the band structure of a l near cha n of hydrogen atoms the bands n th s
system w ll be narrower. Th s s a consequence of the reduced overlap between molecules
( n the prev ous example the molecule was s mply a hydrogen atom).
The net effect of th s d stort on s to lower the energy of the f lled states (wh ch or g nate
from bond ng MO�s) wh le ra s ng the energy of empty states (ant bond ng MO�s). Th s
leads to a net stab l zat on of the system (to calculate the total ground state energy we only
need worry about the occup ed levels). In a 1D system such a d stort on w ll always be
stable when you have a half f lled band (as we d d n the H band structure). Chem sts call
th s a Jahn-Teller d stort on, wh le phys c sts call t a Pe erls d stort on.

Summary

(1) What s be ng plotted?

Energy vs. k : where k s a wavevector that tells us the phase of the AO�s as well as the
wavelength / crystal momentum of an electron n the Yk state.

(2) How many l nes are there n a band structure d agram?

The number of bands s equal to the number of atom c orb tals n the un t cell.

(3) How s the average (center of grav ty) energy level of each band determ ned?

From the MO d agram, due to ntramolecular nteract ons.

(4) Why are some bands w de, others narrow?

Th s s dependent upon the degree of ntermolecular overlap. When the overlap s strong w de
bands result.

(5) How do we determ ne whether a band runs "uph ll" or "downh ll"?

Uph ll bands are bond ng when all orb tals are n phase (k = 0), and ant bond ng when the
orb tals are out of phase (k = p/a). The oppos te holds true for downh ll bands.

(6) How can we tell f a mater al w ll be a metal, an nsulator or a sem conductor?

When EF cuts through a band we expect metall c conduct v ty (though th s s not true when
overlap s negl g ble and bands become very narrow), otherw se we have a sem conductor /
nsulator. In the latter case, EF l es n the m ddle of the band gap.

In summary remember that the band pos t ons are determ ned by the energ es of the atom c
orb tals and the overlap of orb tals w th n a molecule. The w dth of the bands s determ ned by
the overlap of orb tals w th ne ghbor ng molecules ( ntermolecular overlap).

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06.09.2017 Band Structure D agrams

strong ntermolecular overlap à w de bands à delocal zed e- à good conduct v ty

weak ntermolecular overlap à narrow bands à local zed e- à poor conduct v ty

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